CN111948267B - Method for preparing electrochemical nanodot array electrode by using ultra-long nanowires - Google Patents
Method for preparing electrochemical nanodot array electrode by using ultra-long nanowires Download PDFInfo
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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Abstract
A method for preparing an electrochemical nano dot array electrode by using an ultra-long nanowire belongs to the technical field of nano electrode preparation. The invention aims to simply, efficiently and repeatedly prepare the nano dot array electrode, and PDMS is poured on a silicon template containing a micro groove array; pouring resin on the cured PDMS mold to obtain a resin block with a micrometer groove array; depositing a layer of metal film on a resin block, embedding the metal film with resin, performing nano slicing, transferring a single resin sheet containing a nanowire array or a plurality of resin sheets containing the nanowire array which are alternately stacked with empty resin sheets onto a substrate, overlapping and fixing a wire on the surface of the nanowire array, adding resin for encapsulation, repairing and polishing one end of the wire which is not overlapped with the wire to obtain the nano dot array electrode. The invention avoids overlapping of the capacitance and the diffusion layer of the adjacent electrode, and can obtain a new clean nano dot array by repairing and polishing the nano wire end surface again, thereby being beneficial to long-term repeated use of the nano dot array electrode.
Description
Technical Field
The invention belongs to the technical field of nano-electrode preparation, and particularly relates to a method for preparing an electrochemical nano-dot array electrode by using an ultra-long nanowire.
Background
Nanoelectrodes refer to a class of electrodes in which the one-dimensional dimensions of the electrodes are nanoscale. Compared with the conventional electrode, the nano-dot electrode has the following characteristics: the detection limit is very low, and reaches 0.1ng/mL in human hair trace lead measurement; the response speed is extremely high, the time constant is as low as ns level, and the method can be used for measuring the rapid/transient electrochemical reaction; the voltage drop of the electrode is small, and the electrode can be used for electrochemical research of high-impedance medium or electrolyte-free solution; meanwhile, the electrode has extremely small one-dimensional size, so that the object to be detected is not changed in the experimental process, particularly in the process of biological single-molecule detection and single-cell imaging. In general, further reduction of electrochemical nanoelectrode dimensions (down to several nm) can be applied to numerous fields of leading edge basic science, such as transport problems in diffusion layers comparable to the thickness of electric double layers, structures of electric double layers themselves, rapid radial transport conditions caused by competition of reactants/products, molecular reactions with electrode interfaces of similar dimensions, quantum size effects of smaller electrodes, and understanding of electrodeposition and corrosion problems on atomic scale, in addition to the advantages of lower detection limits, faster response times and smaller space for electrical analysis. In the prior art, although there is a preparation method of a nano-electrode with controllable size, for example, a "a nanowire microelectrode with controllable size, a preparation method and an application thereof" is introduced in chinese patent specification CN105675682B issued by patent publication No. 26 of 03 in 2019, so as to realize the controllable preparation of a single linear or circular band-shaped nano-electrode. However, unlike hemispherical diffusion of a disk or spherical nanoelectrode, the diffusion layer of a band-shaped nanoelectrode (macroscopic in the length direction) is semi-cylindrical, which results in a lower mass transfer efficiency of the band-shaped electrode and failure to achieve a true steady state limit state. Meanwhile, the electrochemical voltammetric response of the strip-shaped nano electrode is insensitive to the width change of the electrode, the optimization of the detection limit and the response time is limited, and compensation is needed to be carried out through an extra complex uncontrollable chemical modification step ((such as electrochemical deposition of platinum nano particles on the surface of gold nano wires used in CN 105675682B). The detection limit and the response time belong to the key performance index of the electrochemical electrode, and the application range of the electrochemical voltammetric response is greatly influenced.
Nanoelectrodes have numerous advantages, but their electrochemical response signals are small, typically in the sub-nA to nA range, very sensitive to electrical noise, and standard commercial conventional electrochemical instruments have difficulty measuring their signals, often requiring additional purchase of high quality faraday cages to shield electromagnetic interference, which limits their application in practical sensing devices. In contrast, the nano dot array electrode is formed by combining a plurality of nano dot electrodes (similar to disc-shaped section end faces), so that the characteristics of a single nano dot electrode are maintained, a large current signal (up to hundred and ten mu A) can be obtained, and the standard commodity electrochemical instrument can be used for measurement easily, so that the application range of the nano dot array electrode is greatly widened.
At present, the main preparation methods of the nano dot array electrode are divided into two types: one is a bottom-up method typified by a self-assembly method, a template method, or the like, and the second is a top-down method typified by a chemical etching method, a photolithography method, or the like. The former method has the defects of complex process flow, poor size controllability and the like, and the latter method can prepare the nano dot array electrode with controllable size, but has the defects of high processing equipment cost, low processing efficiency and the like. Therefore, how to simply, efficiently and reproducibly prepare nanodot array electrodes is a major challenge.
Disclosure of Invention
The invention provides a method for preparing an electrochemical nano dot array electrode by using an ultra-long nanowire with controllable size, which aims to simply, efficiently and repeatedly prepare the nano dot array electrode.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for preparing an electrochemical nanodot array electrode by using an ultra-long nanowire, which comprises the following steps:
step one: pouring PDMS on a silicon template containing a micrometer groove array;
step two: pouring resin on the cured PDMS mold to obtain a resin block with a micrometer groove array;
step three: depositing a layer of metal film on the resin block to obtain a metal-resin composite structure;
step four: embedding the composite structure obtained in the step three with resin to obtain a resin-metal-resin embedded block;
step five: performing nano slicing on the embedded block obtained in the step four to obtain a resin sheet containing a nanowire array;
step six: transferring the single resin sheet containing the nanowire array or a plurality of resin sheets containing the nanowire array, which are alternately stacked with the empty resin sheets, obtained in the fifth step to a substrate to obtain a nanowire array-substrate composite structure;
step seven: bonding and fixing the wires on the surface of the nanowire array, adding resin to encapsulate the wire nanowire array, and obtaining a resin-wire-nanowire array-substrate composite structure;
step eight: and D, polishing one end of the lead which is not lapped in the composite structure obtained in the step seven, until the obtained composite structure is subjected to cyclic voltammetry scanning by adopting a three-electrode system, and when the obtained cyclic voltammetry graph is in a standard S shape, the electrode of the nano dot array is successfully prepared.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation of the nano dot array electrode relates to the ultra-thin slicing machine nano slicing technology, the thin film deposition technology, the resin embedding technology, the soft lithography technology and some transfer technologies. The whole preparation process is carried out under normal temperature and normal pressure, the operation of the instrument is simple, the processing cost is low, the efficiency is high, the repeatability is high, the size and the shape of the processed nanowire array are controllable, and the transfer and the positioning are easy. After combining simple alignment technology, the nano dot array electrode with complex structure can be prepared.
(2) The spacing between adjacent nano-dot electrodes is regulated controllably and equidistantly, so that the overlapping of capacitance and diffusion layers of the adjacent electrodes is avoided, and a new clean nano-dot array can be obtained by repairing and polishing the nano-dot end surface again, thereby being beneficial to long-term repeated use of the nano-dot array electrodes.
Drawings
FIG. 1 is a schematic illustration of nanowire array preparation;
FIG. 2 is a schematic illustration of a single-layer nanodot array electrode preparation;
FIG. 3 is a schematic illustration of a multilayer nanodot array electrode fabrication and lap-joint fixation;
fig. 4 is a schematic diagram of electrode lap-joint fixation of a nanodot array.
Detailed Description
The following description of the present invention refers to the accompanying drawings and examples, but is not limited to the same, and modifications and equivalents of the present invention can be made without departing from the spirit and scope of the present invention.
The first embodiment is as follows: the embodiment mode describes a method for preparing an electrochemical nano dot array electrode by using an ultra-long nanowire, which comprises the following steps:
step one: pouring PDMS on a commercial silicon template containing a micro-groove array;
step two: pouring resin on the cured PDMS mold to obtain a resin block with a micrometer groove array;
step three: depositing a layer of metal film on the resin block to obtain a metal-resin composite structure;
step four: embedding the composite structure obtained in the step three with resin to obtain a resin-metal-resin embedded block;
step five: performing nano slicing on the embedded block obtained in the step four to obtain a resin sheet containing a nanowire array;
step six: transferring the single resin sheet containing the nanowire array or a plurality of resin sheets containing the nanowire array, which are alternately stacked with the empty resin sheets, obtained in the fifth step to a substrate to obtain a nanowire array-substrate composite structure;
step seven: bonding and fixing the wires on the surface of the nanowire array, adding resin to encapsulate the wire nanowire array, and obtaining a resin-wire-nanowire array-substrate composite structure;
step eight: and D, polishing one end of the lead which is not lapped in the composite structure obtained in the step seven, until the three-electrode system is adopted to carry out cyclic voltammetry scanning on the obtained composite structure, and when the obtained cyclic voltammetry graph is in a standard S shape, the nano dot array electrode is successfully prepared and can be used in electrochemical experiments.
The second embodiment is as follows: the method for preparing an electrochemical nanodot array electrode by using an ultra-long nanowire in the first embodiment comprises the step of forming a metal film with a thickness of 2 nm-1 μm.
And a third specific embodiment: in the method for preparing the electrochemical nanodot array electrode by using the ultra-long nanowire according to the first or second embodiment, in the first step, the metal is one of gold, platinum or silver.
The specific embodiment IV is as follows: the method for preparing the electrochemical nanodot array electrode by using the ultra-long nanowire in the first embodiment comprises the following steps of, in the second, fourth and seventh steps, the resin is thermosetting resin.
Fifth embodiment: in the method for preparing the electrochemical nano dot array electrode by using the ultra-long nanowire, in the fifth step, the nano slicing is carried out by adopting an ultra-thin slicing machine, firstly, a block repairing cutter matched with an instrument is used for repairing and polishing an embedded block to expose the end face of a metal film, then the embedded block containing the metal film is trimmed into a trapezoid or square boss, the length of each side is 0.2-4 mm, a straight-line edge glass cutter or a diamond cutter matched with the instrument is used for slicing the boss containing the metal film, the groove liquid of a cutter water groove is double distilled water, the slicing speed is 0.1-10 mm/s, the slicing direction is parallel to the surface of the metal microarray, and the slicing thickness is 20 nm-15 mu m. The model of the ultrathin slicer is Leica UC7.
Specific embodiment six: in the method for preparing the electrochemical nanodot array electrode by using the ultra-long nanowires, in the sixth step, the transfer is realized by a drag-out ring drag-out piece of the instrument.
Seventh embodiment: the method for preparing the electrochemical nanodot array electrode by using the ultra-long nanowires in the sixth embodiment transfers the resin sheet from the water tank to the surface of the substrate, and uses the hair fiber pen matched with the instrument to controllably micro-adjust the resin sheet under the split type light mirror.
Eighth embodiment: in the method for preparing the electrochemical nanodot array electrode by using the ultra-long nanowire, in the seventh step, the lead is lapped by copper foil, the fixing mode is bonding, wherein the lapping material is conductive silver adhesive, and the fixing material is AB adhesive.
Detailed description nine: in the method for preparing the electrochemical nanodot array electrode by using the ultra-long nanowire, in the eighth step, the block repairing and polishing are performed by adopting an ultra-thin slicer, firstly, the whole end surface of the embedded block is repaired by using a glass block repairing knife matched with an instrument, then, the diamond block repairing knife is used for finely repairing the nanowire area, and the end surface of the nanowire is exposed.
Detailed description ten: in the method for preparing the electrochemical nanodot array electrode by using the ultra-long nanowire, in the eighth step, in the three-electrode system, the reference electrode is Ag/AgCl (saturated KCl), and the counter electrode is Pt wire; the cyclic voltammetry scanning specifically comprises the following steps: and placing the nano dot array electrode in 1mmol/L ferrocene methanol aqueous solution for cyclic voltammetry scanning, wherein the supported electrolyte is a KCl aqueous solution with the concentration of 0.5mol/L, the potential range is-0.1V-0.6V, and the scanning rate is 0.1V/s.
The invention mainly uses an ultra-thin slicer as processing equipment, combines a soft lithography technology and a thin film deposition technology to controllably prepare an ultra-long nanowire array, and obtains the nano-dot array electrode by simply lapping micro-wires and performing insulation packaging treatment.
Example 1:
the preparation of the single-layer gold nano dot array electrode, as shown in fig. 1 and 2, comprises the following specific operation steps:
step one: preparation of sample for slicing
(1) And pouring PDMS prepolymer into a commercial silicon template containing a 5 mu m micrometer groove array for curing to obtain the PDMS mold. PDMS and curing agent are mixed according to the mass ratio of 10:1, fully mixed for 10min, placed in a vacuum dryer for 30min degassing treatment, and cured in an oven at 80 ℃ for 3 hours.
(2) And placing epoxy resin Epo-fix resin prepolymer on the surface of a PDMS mold, and obtaining the resin block containing the micro-groove array through a transfer printing technology. Mixing the resin and the curing agent according to the mass ratio of 15:2, stirring slowly for 2min in one direction, and placing in a vacuum dryer for degassing treatment for 30 min. Then pouring the resin into a container for containing the substrate slowly, covering the whole gold film, and solidifying for 2-3 hours at 60 ℃.
(3) Placing the resin block containing the micro-groove array in a vacuum coating system, and vacuum-coating at a vacuum degree of 1×10 -3 Under Pa condition, adopting electron beam vapor deposition to deposit metal gold, wherein the deposition rate is 0.8 to the whole range1nm/s, and the thickness of the prepared gold film is 100nm.
(4) And stripping the cured resin from the substrate, and separating and firmly attaching the gold film on the surface of the resin under the action of adhesion force.
(5) And (3) cutting the gold film-resin composite structure properly, placing the gold film-resin composite structure in a silica gel embedding mold, pouring resin prepolymer to cover the gold film, and curing for 2-3 hours at 60 ℃ to obtain a cuboid embedding block sample with the size of 14 multiplied by 5 multiplied by 3mm (length multiplied by width multiplied by height).
Step two: preparing a nanowire array by a nano slicing method: and (5) performing block repairing and nano slicing treatment on the sample by using an ultrathin slicer. Firstly, a block repairing knife is used for repairing and polishing the embedded block to expose the end face of the gold film, and then the embedded block containing the metal film part is trimmed into a trapezoid boss, and the length of each side is 0.6mm. Cutting the boss of the gold-containing film by using a straight-line blade glass knife, wherein the groove liquid of the cutter water groove is double distilled water, the cutting speed is 1mm/s, the cutting direction is parallel to the surface of the metal microstructure, and the cutting thickness is 100nm.
Step three: transfer and control of nanowire arrays: the instrument is adopted to drag out the slice by a slice dragging ring, the resin slice is transferred from the water tank to the surface of the substrate after hydrophilic treatment, and the hair fiber pen is used for controllable micro-adjustment of the resin slice under the split type light mirror.
Step four: lapping and fixing of micro wires: as shown in fig. 4, a copper foil with the thickness of 0.1mm is lapped on one side of the upper surface of the nanowire, and a conductive silver adhesive is used for connecting a wire and the nanowire so as to ensure current conduction; the AB glue was used as a fixing material to adhere the copper foil to the resin surface.
Step five: packaging of single-layer gold nano dot array electrodes: and placing the obtained sample in a silica gel embedding mould, pouring resin prepolymer to cover the nanowire array and the wires, and curing for 2-3 hours at 60 ℃ to obtain a well-packaged single-layer gold nano dot array electrode sample.
Step six: polishing of the nano dot array electrode: carrying out block repairing and polishing treatment on the obtained sample by adopting an ultrathin slicer, firstly using a glass cutter to repair one end of the embedded block, which is not lapped with the lead, wherein the block repairing speed is 100mm/s, and the block repairing thickness is 150nm; and then replacing a 45-degree diamond trimming cutter to carry out fine trimming on the nanowire region, wherein the trimming speed is 80mm/s, the trimming thickness is 100nm, the end face of the nanowire array is exposed, the end face size of the obtained nanowire is 100 multiplied by 100nm, namely the size of the nanowire is the size of the nanowire, and the distance between the nanowire and the nanowire is 5 mu m.
Step seven: characterization of single-layer gold nanodot array electrode: and (3) carrying out cyclic voltammetry scanning on the nano dot array electrode in a ferrocene methanol aqueous solution with the concentration of 1mmol/L, wherein the supported electrolyte is a KCl aqueous solution with the concentration of 0.5mol/L, the potential range is-0.1V-0.6V, the scanning rate is 0.1V/S, and the cyclic voltammetry graph obtained by detection is in a standard S shape, so that the nano dot array electrode is successfully prepared.
Example 2:
the preparation of the single-layer platinum nano dot array electrode, as shown in fig. 1 and 2, comprises the following specific operation steps:
step one: preparation of sample for slicing
(1) And pouring PDMS prepolymer into a commercial silicon template containing an 8-mu m micrometer groove array for curing to obtain the PDMS mold. PDMS and curing agent are mixed according to the mass ratio of 10:1, fully mixed for 10min, placed in a vacuum dryer for 30min degassing treatment, and cured in an oven at 80 ℃ for 3 hours.
(2) And placing epoxy resin Epo-fix resin prepolymer on the surface of a PDMS mold, and obtaining the resin block containing the micro-groove array through a transfer printing technology. Mixing the resin and the curing agent according to the mass ratio of 15:2, stirring slowly for 2min in one direction, and placing in a vacuum dryer for degassing treatment for 30 min. Then pouring the resin into a container for containing the substrate slowly, covering the whole gold film, and solidifying for 2-3 hours at 60 ℃.
(3) Placing the resin block containing the micro-groove array in a vacuum coating system, and vacuum-coating at a vacuum degree of 1×10 -3 Under Pa, adopting electron beam vapor deposition to deposit metal platinum, wherein the deposition rate is 0.4-0.5 nm/s, and the thickness of the prepared platinum film is 200nm.
(4) And stripping the cured resin from the substrate, and separating and firmly attaching the platinum film on the surface of the resin under the action of adhesion force.
(5) And (3) cutting the platinum film-resin composite structure properly, placing the platinum film-resin composite structure in a silica gel embedding mold, pouring resin prepolymer to cover the platinum film, and curing for 2-3 hours at 60 ℃ to obtain a cuboid embedding block sample with the size of 14 multiplied by 5 multiplied by 3mm (length multiplied by width multiplied by height).
Step two: preparing a nanowire array by a nano slicing method: and (5) performing block repairing and nano slicing treatment on the sample by using an ultrathin slicer. Firstly, a block repairing knife is used for repairing and polishing the embedded block, the end face of the platinum film is exposed, and then the embedded block containing the metal film part is trimmed into a trapezoid boss, and the length of each side is 0.8mm. Cutting the lug boss of the platinum-containing film by using a linear blade diamond knife, wherein the groove liquid of the cutter water groove is double distilled water, the cutting speed is 0.5mm/s, the cutting direction is parallel to the surface of the metal microstructure, and the cutting thickness is 200nm.
Step three: transfer and control of nanowire arrays: the instrument is adopted to drag out the slice by a slice dragging ring, the resin slice is transferred from the water tank to the surface of the substrate after hydrophilic treatment, and the hair fiber pen is used for controllable micro-adjustment of the resin slice under the split type light mirror.
Step four: lapping and fixing of micro wires: as shown in fig. 4, a copper foil with the thickness of 0.1mm is lapped on one side of the upper surface of the nanowire, and a conductive silver adhesive is used for connecting a wire and the nanowire so as to ensure current conduction; the AB glue was used as a fixing material to adhere the copper foil to the resin surface.
Step five: packaging of single-layer platinum nano dot array electrodes: and placing the obtained sample in a silica gel embedding mould, pouring resin prepolymer to cover the nanowire array and the wires, and curing for 2-3 hours at 60 ℃ to obtain a well-packaged single-layer platinum nano-dot array electrode sample.
Step six: polishing of the nano dot array electrode: carrying out block repairing and polishing treatment on the obtained sample by adopting an ultrathin slicer, firstly using a glass cutter to repair one end of the embedded block, which is not lapped with the lead, wherein the block repairing speed is 100mm/s, and the block repairing thickness is 150nm; and then replacing a 45-degree diamond trimming cutter to carry out fine trimming on the nanowire region, wherein the trimming speed is 80mm/s, the trimming thickness is 100nm, the end face of the nanowire array is exposed, the end face size of the obtained nanowire is 200 multiplied by 200nm, namely the size of the nano dot, and the distance between the nano dots is 8 mu m.
Step seven: characterization of single-layer platinum nanodot array electrode: and (3) carrying out cyclic voltammetry scanning on the nano dot array electrode in a ferrocene methanol aqueous solution with the concentration of 1mmol/L, wherein the supported electrolyte is a KCl aqueous solution with the concentration of 0.5mol/L, the potential range is-0.1V-0.6V, the scanning rate is 0.1V/S, and the cyclic voltammetry graph obtained by detection is in a standard S shape, so that the nano dot array electrode is successfully prepared.
Example 3:
the preparation of the three-layer gold nano dot array electrode, as shown in fig. 3, comprises the following specific operation steps:
step one: preparation of sample for slicing
(1) And pouring PDMS prepolymer into a commercial silicon template containing a 2 mu m micrometer groove array for curing to obtain the PDMS mold. PDMS and curing agent are mixed according to the mass ratio of 10:1, fully mixed for 10min, placed in a vacuum dryer for 30min degassing treatment, and cured in an oven at 80 ℃ for 3 hours.
(2) And placing epoxy resin Epo-fix resin prepolymer on the surface of a PDMS mold, and obtaining the resin block containing the micro-groove array through a transfer printing technology. Mixing the resin and the curing agent according to the mass ratio of 15:2, stirring slowly for 2min in one direction, and placing in a vacuum dryer for degassing treatment for 30 min. Then pouring the resin into a container for containing the substrate slowly, covering the whole gold film, and solidifying for 2-3 hours at 60 ℃.
(3) Placing the resin block containing the micro-groove array in a vacuum coating system, and vacuum-coating at a vacuum degree of 1×10 -3 Under Pa, adopting electron beam evaporation to deposit metal gold, wherein the deposition rate is 0.8-1 nm/s, and the thickness of the prepared gold film is 50nm.
(4) And stripping the cured resin from the substrate, and separating and firmly attaching the gold film on the surface of the resin under the action of adhesion force.
(5) And (3) cutting the gold film-resin composite structure properly, placing the gold film-resin composite structure in a silica gel embedding mold, pouring resin prepolymer to cover the gold film, and curing for 2-3 hours at 60 ℃ to obtain a cuboid embedding block sample with the size of 14 multiplied by 5 multiplied by 3mm (length multiplied by width multiplied by height).
Step two: preparing a nanowire array by a nano slicing method: and (5) performing block repairing and nano slicing treatment on the sample by using an ultrathin slicer. Firstly, a block repairing knife is used for repairing and polishing the embedded block, the end face of the gold film is exposed, and then the embedded block containing the metal film part is trimmed into square bosses, and the length of each side is 0.5mm. Cutting the boss of the gold-containing film by using a straight-line edge diamond knife, wherein the groove liquid of the cutter water groove is double distilled water, the cutting speed is 1mm/s, the cutting direction is parallel to the surface of the metal microstructure, and the cutting thickness is 50nm.
Step three: transfer and control of single-layer nanowire arrays: the instrument is adopted to drag out the slice by a slice dragging ring, the resin slice containing the nanowire array is transferred from the water tank to the surface of the substrate after hydrophilic treatment, and the resin slice is controllably micro-regulated by a hair fiber pen under the split type light mirror.
Step four: preparation and transfer of empty resin: preparing an Epo-fix resin block, and trimming the end face of the resin block into square bosses with the length of each side of 0.5 mu m by using an ultra-thin slicer. The slicing speed was 1mm/s and the slicing thickness was 2. Mu.m. And 3, adopting a drag-out ring of the instrument to drag out the resin sheet, transferring the empty resin sheet without the nanowire array from the water tank to the surface of the resin sheet in the third step, and using a hair fiber pen to controllably micro-adjust the resin sheet under the split type light mirror to enable the resin sheet to be basically overlapped with the lower resin sheet.
Step five: second layer nanowire array transfer and control: and controllably stacking the resin sheet containing the nanowire array on the surface of the empty resin sheet obtained in the step four.
Step six: multi-layered nanowire array transfer and control: and repeating the step four and the step five once respectively to obtain a three-layer nanowire array with an upper-lower interval of 2 mu m and a left-right interval of 2 mu m.
Step seven: lapping and fixing of micro wires: as shown in fig. 4, a copper foil with the thickness of 0.2mm is lapped on one side of the upper surface of the nanowire, and a conductive silver adhesive is used for connecting a wire with the nanowire so as to ensure current conduction; the AB glue was used as a fixing material to adhere the copper foil to the resin surface.
Step eight: packaging of the multilayer gold nano dot array electrode: and placing the obtained sample in a silica gel embedding mould, pouring resin prepolymer to cover the nanowire array and the wires, and curing for 2-3 hours at 60 ℃ to obtain a three-layer gold nano dot array electrode sample well packaged.
Step nine: polishing of the nano dot array electrode: carrying out block repairing and polishing treatment on the obtained sample by adopting an ultrathin slicer, firstly using a glass cutter to repair one end of the embedded block, which is not lapped with the lead, wherein the block repairing speed is 100mm/s, and the block repairing thickness is 150nm; and then replacing a 45-degree diamond trimming cutter to carry out fine trimming on the nanowire region, wherein the trimming speed is 80mm/s, the trimming thickness is 100nm, the end face of the nanowire array is exposed, the end face size of the obtained nanowire is 50 multiplied by 50nm, namely the size of the nanowire is the size of the nanowire, and the distance between the nanowire and the nanowire is 2 mu m.
Step ten: characterization of three-layer gold nanodot array electrodes: and (3) carrying out cyclic voltammetry scanning on the three-layer gold nano dot array electrode in 1mmol/L ferrocene methanol aqueous solution, wherein the supported electrolyte is 0.5mol/L KCl aqueous solution, the potential range is-0.1V-0.6V, the scanning rate is 0.1V/S, and the cyclic voltammetry graph obtained by detection is in a standard S shape, so that the nano dot array electrode is successfully prepared.
Example 4:
the preparation of the five-layer platinum nano dot array electrode, as shown in fig. 3, comprises the following specific operation steps:
step one: preparation of sample for slicing
(1) And pouring PDMS prepolymer into a commercial silicon template containing a 3 mu m micrometer groove array for curing to obtain the PDMS mold. PDMS and curing agent are mixed according to the mass ratio of 10:1, fully mixed for 10min, placed in a vacuum dryer for 30min degassing treatment, and cured in an oven at 80 ℃ for 3 hours.
(2) And placing epoxy resin Epo-fix resin prepolymer on the surface of a PDMS mold, and obtaining the resin block containing the micro-groove array through a transfer printing technology. Mixing the resin and the curing agent according to the mass ratio of 15:2, stirring slowly for 2min in one direction, and placing in a vacuum dryer for degassing treatment for 30 min. Then pouring the resin into a container for containing the substrate slowly, covering the whole gold film, and solidifying for 2-3 hours at 60 ℃.
(3) Will contain micro-groove arrayThe resin blocks in the rows are placed in a vacuum coating system, and the vacuum degree is 1 multiplied by 10 -3 Under Pa, adopting electron beam vapor deposition to deposit metal platinum, wherein the deposition rate is 0.4-0.5 nm/s, and the thickness of the prepared platinum film is 150nm.
(4) And stripping the cured resin from the substrate, and separating and firmly attaching the platinum film on the surface of the resin under the action of adhesion force.
(5) And (3) cutting the platinum film-resin composite structure properly, placing the platinum film-resin composite structure in a silica gel embedding mold, pouring resin prepolymer to cover the platinum film, and curing for 2-3 hours at 60 ℃ to obtain a cuboid embedding block sample with the size of 14 multiplied by 5 multiplied by 3mm (length multiplied by width multiplied by height).
Step two: preparing a nanowire array by a nano slicing method: and (5) performing block repairing and nano slicing treatment on the sample by using an ultrathin slicer. Firstly, a block repairing knife is used for repairing and polishing the embedded block, the end face of the platinum film is exposed, and then the embedded block containing the metal film part is trimmed into square bosses, and the length of each side is 1mm. Cutting the boss of the gold-containing film by using a straight-line edge diamond knife, wherein the groove liquid of the cutter water groove is double distilled water, the cutting speed is 0.3mm/s, the cutting direction is parallel to the surface of the metal microstructure, and the cutting thickness is 150nm.
Step three: transfer and control of single-layer nanowire arrays: the instrument is adopted to drag out the slice by a slice dragging ring, the resin slice containing the nanowire array is transferred from the water tank to the surface of the substrate after hydrophilic treatment, and the resin slice is controllably micro-regulated by a hair fiber pen under the split type light mirror.
Step four: preparation and transfer of empty resin: preparing an Epo-fix resin block, and trimming the end face of the resin block into square bosses with the length of each side of 0.5 mu m by using an ultra-thin slicer. The slicing speed was 1mm/s and the slicing thickness was 3. Mu.m. And 3, adopting a drag-out ring of the instrument to drag out the resin sheet, transferring the empty resin sheet without the nanowire array from the water tank to the surface of the resin sheet in the third step, and using a hair fiber pen to controllably micro-adjust the resin sheet under the split type light mirror to enable the resin sheet to be basically overlapped with the lower resin sheet.
Step five: second layer nanowire array transfer and control: and controllably stacking the resin sheet containing the nanowire array on the surface of the empty resin sheet obtained in the step four.
Step six: multi-layered nanowire array transfer and control: repeating the step four and the step five three times respectively to obtain five-layer nanowire arrays with the vertical interval of 3 mu m and the left and right interval of 3 mu m.
Step seven: lapping and fixing of micro wires: as shown in fig. 4, a copper foil with the thickness of 0.2mm is lapped on one side of the upper surface of the nanowire, and a conductive silver adhesive is used for connecting a wire with the nanowire so as to ensure current conduction; the AB glue was used as a fixing material to adhere the copper foil to the resin surface.
Step eight: packaging of the multilayer platinum nano dot array electrode: and placing the obtained sample in a silica gel embedding mould, pouring resin prepolymer to cover the nanowire array and the wires, and curing for 2-3 hours at 60 ℃ to obtain a well-packaged five-layer platinum nano dot array electrode sample.
Step nine: polishing of the nano dot array electrode: carrying out block repairing and polishing treatment on the obtained sample by adopting an ultrathin slicer, firstly using a glass cutter to repair one end of the embedded block, which is not lapped with the lead, wherein the block repairing speed is 100mm/s, and the block repairing thickness is 150nm; and then replacing a 45-degree diamond block trimming cutter to carry out fine block trimming on the nanowire area, wherein the block trimming speed is 80mm/s, the block trimming thickness is 100nm, the end face of the nanowire array is exposed, the end face size of the obtained nanowire is 150 multiplied by 150nm, namely the size of the nano point, and the distance between the nano points is 3 mu m.
Step ten: characterization of five-layer platinum nanodot array electrode: and (3) carrying out cyclic voltammetry scanning on the five-layer platinum nano dot array electrode in 1mmol/L ferrocene methanol aqueous solution, wherein the supported electrolyte is a KCl aqueous solution with the concentration of 0.5mol/L, the potential range is-0.1V-0.6V, the scanning rate is 0.1V/S, and the cyclic voltammetry graph obtained by detection is in a standard S shape, so that the nano dot array electrode is successfully prepared.
Claims (9)
1. A method for preparing an electrochemical nano dot array electrode by using an ultra-long nanowire is characterized in that: the method comprises the following steps:
step one: pouring PDMS on a silicon template containing a micrometer groove array;
step two: pouring resin on the cured PDMS mold to obtain a resin block with a micrometer groove array;
step three: depositing a layer of metal film on the resin block to obtain a metal-resin composite structure;
step four: embedding the composite structure obtained in the step three with resin to obtain a resin-metal-resin embedded block;
step five: performing nano slicing on the embedded block obtained in the step four to obtain a resin sheet containing a nanowire array; the nano slicing is carried out by adopting an ultrathin slicing machine, firstly, a block repairing knife matched with an instrument is used for repairing and polishing an embedded block to expose the end face of a metal film, then the embedded block containing the metal film is trimmed into trapezoidal or square bosses, the length of each side is 0.2-4 mm, a straight-line blade glass knife or a diamond knife matched with the instrument is used for slicing the bosses containing the metal film, the groove liquid of a cutter water groove is double distilled water, the slicing speed is 0.1-10 mm/s, the slicing direction is parallel to the surface of a metal microarray, and the slicing thickness is 20 nm-15 mu m;
step six: transferring the single resin sheet containing the nanowire array obtained in the step five to a substrate to obtain a nanowire array-substrate composite structure;
step seven: bonding and fixing the wires on the surface of the nanowire array, adding resin to encapsulate the wire nanowire array, and obtaining a resin-wire-nanowire array-substrate composite structure;
step eight: and D, polishing one end of the lead which is not lapped in the composite structure obtained in the step seven, until the obtained composite structure is subjected to cyclic voltammetry scanning by adopting a three-electrode system, and when the obtained cyclic voltammetry graph is in a standard S shape, the electrode of the nano dot array is successfully prepared.
2. A method of preparing an electrochemical nanodot array electrode using ultra-long nanowires as recited in claim 1, wherein: in the third step, the thickness of the metal film is 2 nm-1 μm.
3. A method for preparing an electrochemical nanodot array electrode using ultra-long nanowires according to claim 1 or 2, wherein: in the third step, the metal is one of gold, platinum or silver.
4. A method of preparing an electrochemical nanodot array electrode using ultra-long nanowires as recited in claim 1, wherein: in the second, fourth and seventh steps, the resin is a thermosetting resin.
5. A method of preparing an electrochemical nanodot array electrode using ultra-long nanowires as recited in claim 1, wherein: in the sixth step, the transfer is realized by a drag-out ring drag-out piece of the instrument.
6. The method for preparing the electrochemical nanodot array electrode by using the ultra-long nanowire according to claim 5, wherein: transferring the resin sheet from the water tank to the surface of the substrate, and performing controllable micro-adjustment on the resin sheet under the split mirror by using a hair fiber pen matched with the instrument.
7. A method of preparing an electrochemical nanodot array electrode using ultra-long nanowires as recited in claim 1, wherein: in the seventh step, the lead is lapped by copper foil, the fixing mode is bonding, wherein the lapping material is conductive silver adhesive, and the fixing material is AB adhesive.
8. A method of preparing an electrochemical nanodot array electrode using ultra-long nanowires as recited in claim 1, wherein: in the eighth step, the block repairing and polishing are carried out by adopting an ultrathin slicer, firstly, a glass block repairing knife matched with an instrument is used for repairing the whole end face of the embedded block, and then a diamond block repairing knife is used for finely repairing the nanowire area to expose the end face of the nanowire.
9. A method of preparing an electrochemical nanodot array electrode using ultra-long nanowires as recited in claim 1, wherein: in the eighth step, in the three-electrode system, the reference electrode is Ag/AgCl, and the counter electrode is Pt wire; the cyclic voltammetry scanning specifically comprises the following steps: and placing the nano dot array electrode in 1mmol/L ferrocene methanol aqueous solution for cyclic voltammetry scanning, wherein the supported electrolyte is a KCl aqueous solution with the concentration of 0.5mol/L, the potential range is-0.1V-0.6V, and the scanning rate is 0.1V/s.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001070873A2 (en) * | 2000-03-22 | 2001-09-27 | University Of Massachusetts | Nanocylinder arrays |
| WO2007041293A2 (en) * | 2005-09-29 | 2007-04-12 | Doheny Eye Institute | Microelectrode systems for neuro-stimulation and neuro-sensing and microchip packaging and related methods |
| CN101051033A (en) * | 2007-05-15 | 2007-10-10 | 中国科学院长春应用化学研究所 | Method for preparing micro disc electrode or micro disc array electrode |
| WO2008018923A2 (en) * | 2006-03-22 | 2008-02-14 | President And Fellows Of Harvard College | Fabrication of isolated nanostructures and/or arrays of nanostructures |
| CN101225515A (en) * | 2007-10-17 | 2008-07-23 | 哈尔滨工业大学（威海） | Method for preparing gold-nano array electrode |
| WO2015120011A1 (en) * | 2014-02-04 | 2015-08-13 | N12 Technologies, Inc. | Articles and methods for manufacture of nanostructure reinforced composites |
| CN107541488A (en) * | 2017-09-15 | 2018-01-05 | 盐城师范学院 | A kind of method based on Crystal structure guiding cell behavior |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8187865B2 (en) * | 2003-06-12 | 2012-05-29 | California Institute Of Technology | Nanowire sensor, sensor array, and method for making the same |
| WO2005010518A1 (en) * | 2003-07-23 | 2005-02-03 | Dexcom, Inc. | Rolled electrode array and its method for manufacture |
| CN1223849C (en) * | 2003-11-17 | 2005-10-19 | 中国科学院长春应用化学研究所 | Preparing method of micro disk array electrode |
| WO2009011975A2 (en) * | 2007-05-23 | 2009-01-22 | California Institute Of Technology | Method for fabricating monolithic two-dimensional nanostructures |
| AU2011329283B2 (en) * | 2010-11-15 | 2014-09-25 | The Government of the United State of America, as represented by the Secretary of the Navy | Perforated contact electrode on vertical nanowire array |
| CN105675682B (en) * | 2015-12-28 | 2019-03-26 | 中国人民大学 | A kind of nano wire microelectrode and the preparation method and application thereof that size is controllable |
| CN106006546B (en) * | 2016-07-01 | 2017-07-11 | 吉林大学 | A kind of method for shifting and controlling nanostructured |
-
2020
- 2020-08-20 CN CN202010844645.9A patent/CN111948267B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001070873A2 (en) * | 2000-03-22 | 2001-09-27 | University Of Massachusetts | Nanocylinder arrays |
| WO2007041293A2 (en) * | 2005-09-29 | 2007-04-12 | Doheny Eye Institute | Microelectrode systems for neuro-stimulation and neuro-sensing and microchip packaging and related methods |
| WO2008018923A2 (en) * | 2006-03-22 | 2008-02-14 | President And Fellows Of Harvard College | Fabrication of isolated nanostructures and/or arrays of nanostructures |
| CN101051033A (en) * | 2007-05-15 | 2007-10-10 | 中国科学院长春应用化学研究所 | Method for preparing micro disc electrode or micro disc array electrode |
| CN101225515A (en) * | 2007-10-17 | 2008-07-23 | 哈尔滨工业大学（威海） | Method for preparing gold-nano array electrode |
| WO2015120011A1 (en) * | 2014-02-04 | 2015-08-13 | N12 Technologies, Inc. | Articles and methods for manufacture of nanostructure reinforced composites |
| CN107541488A (en) * | 2017-09-15 | 2018-01-05 | 盐城师范学院 | A kind of method based on Crystal structure guiding cell behavior |
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